The high power laser development required the need of materials with nonlinear properties. Glass materials can be considered as ideal materials as they can be transparent and elaborated in very large dimension. Precipitation of non-centro symmetric crystalline particles in bulk glass leads to a material with bulk nonlinear properties. This glass-ceramic should be then easily integrated in such laser facilities. In this thesis, the results concerning the precipitation of the LiNO3 phase in the glassy-matrix 35 Li2O- 25 Nb2O5- 40 SiO2 are detailed. The crystallization mechanism of this phase is studied through thermal analysis, optical and electronic microscopy as well as in-situ analyses. These studies reveal glass-ceramics are obtained through a precipitation of the lithium niobate crystalline phase in spherulite shape. The nonlinear optical properties are investigated on this materials and an original, isotropic Second Harmonic Generation signal (SHG) is registered in the bulk glass-ceramic. A complete study using a multi-scale approach allows the correlation between the spherulite structure and the nonlinear optical properties. A mechanism at the origin of the SHG signal is proposed. This leads to a new approach for transparent inorganic materials development for isotropic SHG conversion.
